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Mechanism of the catalytic carboxylation of alkylboronates with CO2 using Ni-NHC complexes: A DFT Study

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Author(s)

Maicon Delarmelina, Enrico Marelli, Jose Carneiro, Steven Nolan, Michael Buehl

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Abstract

A new mechanism is proposed for the Ni-catalysed carboxylation of organoboronates with CO2. DFT investigations at the PBE0-D3 level have shown that direct CO2 addition to the catalysts [Ni(NHC)(Allyl)Cl] (1NHC, NHC = IMe, IPr, SIPr and IPr*) is kinetically disfavored and formation of the Aresta-type intermediate is unlikely to occur. According to the mechanism proposed here, the carboxylation process starts with addition of the borate species to 1NHC, followed by transmetalation, CO2 cycloaddition and carboxylation. The rate-determining step was identified as being the transmetalation process, with computed relative free energy barriers of 34.8, 36.8 and 33.5 kcal mol-1 for 1IPr, 1SIPr and 1IPr*, respectively
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Original languageEnglish
JournalChemistry - A European Journal
VolumeIn press
DOIs
StateAccepted/In press - 29 Aug 2017

    Research areas

  • Carbene ligands, Nickel, N-Heterocyclic carbene, Carbon dioxide, Carboxylation, DFT

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